Effect of surfactants on the rate of solid-liquid mass transfer with gas generation at the interface

The effect of Triton X-100 (nonionic surfactant) and cetyltrimethylammonium bromide (CTAB), cationic surfactant, on the mass transfer coefficient of the cathodic reduction of ferricyanide ions and anodic oxidation of ferrocyanide ions at hydrogen- and oxygen-evolving electrodes, respectively, was studied. It was found that the limiting current decreases by amounts ranging from 26.67 to 54.67% for Triton X-100 and from 20 to 46.0% for CTAB in the case of cathodic reduction of ferricyanide ions under natural convection at H2-evolving electrodes and from 23.81 to 51.43% for Triton X-100 and from 18.10 to 40.95% for CTAB in the case of anodic oxidation of ferrocyanide ions under natural convection at O2-evolving electrodes, depending on the concentration of surfactant. Also the effects of Triton X-100 and CTAB on the gas hold-up and cell voltage were studied. The presence of surfactant in electrolytes was found to decrease the mass transfer coefficient by an amount ranging from 5.37 to 95.9%, depending on the operating conditions. Gas hold-up, cell voltage, and power consumption were found to increase in the presence of surfactant.     

固体粒子对板式膜吸收过程的传质强化

分别采用纯CO2-去离子水和不同浓度的NaOH溶液为实验体系,在板式膜器中研究了第三相固体粒子对膜吸收过程传质效果的影响．分别考察了在不同粒子种类、搅拌转速、传质体系、化学反应强度、膜孔隙率等因素下固体粒子对传质强化的影响．结果表明,随着粒子固含率的增大,传质系数和增强因子均有所提高,当粒子固含率增大到一定范围后,传质系数和增强因子的变化趋于平缓．在固含率一定的条件下,不同种类的固体粒子对膜吸收过程的强化效果随着固体粒子密度的增加而减小．传质系数随着搅拌转速的增大而增大,但高搅拌转速下固体粒子的强化作用减弱．膜吸收过程的传质系数和增强因子随着化学反应强度的增强而增加．随着粒子固含率的增大,不同膜孔隙率对传质效果的差异减小,且孔隙率越小,固体粒子对膜吸收传质过程的强化效果越好．其中,对于纯CO2-去离子水体系,当孔隙率为20％,粒子固含率为1．5gL^（-1）时,固体粒子的加入可使传质系数提高1．45倍,增强因子可达2．45．     

Enhancement of oxygen gas–liquid mass transfer with colloidal gas aphron dispersions

In this work, an attempt was made to enhance gas–liquid mass transfer of oxygen with the aid of colloidal gas aphron (CGA) dispersion. The gas–liquid volume mass transfer coefficients (k_La) of oxygen in CGA dispersions were measured and related to stirring velocity, type and concentration of surfactants, and temperature. Four surfactants, sodium dodecyl sulfate (SDS), hexadecyltrimethyl ammonium chloride (HTAC), nonylphenol ethoxylate (NP-10), and potassium mono lauryl phosphate (MAPK), were examined in forming CGAs and thereby affecting the mass transfer of oxygen in the dispersions. It was found that effects of surfactants on the oxygen gas–liquid mass transfer were type-dependent. As concentrations rose, the k_La of oxygen increased evidently for SDS and an enhancement of k_La by a factor of three was observed at the concentration of 2.75 g/L. However the k_La decreased for MAPK. Nonylphenol ethoxylate was found to have little effect on k_La and HTAC showed mixed behavior. In SDS dispersion, it was found that the mass transfer reached a maximum value at a stirring velocity of 8000 r/min, but further benefit was not observed afterwards. With the increase of temperature, the mass transfer of oxygen was intensified but no much benefit was observed above 308 K.     

SDS/n-C5H11OH/H2O溶致液晶中SDS分子的扩散特性

以铂微电极法测定了在SDS/n-C5H11OH/H2O溶致液晶中SDS（十二烷基硫酸钠）分子的扩散系数.结果表明,恒定质量比SDS/n-C5H11OH条件下,溶致液晶中SDS分子的扩散系数随体系中水含量的增加而增加；恒定质量比SDS/H2O,溶致液晶中SDS分子的扩散系数随正戊醇含量的增加而增加；恒定质量比H2O/n-C5H11OH ,溶致液晶中SDS分子的扩散系数随SDS含量的增加而降低.六角状液晶中SDS分子的扩散系数比层状液晶中SDS分子的扩散系数低约1个数量级,而比W/O、O/W胶束的扩散系数低3～5个数量级.     

Effect of Sodium dodecyl sulfate on the Mass Transfer Rate between Styrene and Water

Summary: The effect of sodium dodecyl sulfate (SDS) on the mass transfer rate between styrene and water has been investigated. SDS increases the solubility of styrene in water even below the critical micelle concentration (CMC) and therefore increases the thermodynamic driving force for the mass transfer. The mass transfer coefficient however is not altered by SDS, even if the interface is almost saturated with emulsifier.     

Influence of suspended solid particles on gas-liquid mass transfer coefficient in a system stirred by double impellers

The aim of the research work was to investigate the effect of the presence and concentration of solid particles on the gas-liquid volumetric mass transfer coefficient in a mechanically stirred gas-solid-liquid system. Experimental studies were conducted in a tall vessel of the diameter of 0.288 m, equipped with two designs of double stirrers. Three high-speed stirrers were used: A 315, Smith turbine, and Rushton turbine. The following operating parameters were changed: gas flow rate, stirrer speed, and solid concentration. The volumetric mass transfer coefficient was determined using the dynamic gassing-out method. In the range of the measurements conducted, this coefficient was strongly affected by both the presence and the concentration of particles in the system. Generally, a low concentration of particles in the system, equal to 0.5 mass %, caused an increase of the volumetric mass transfer coefficient values for both stirrer configurations compared to a system without solids whilst more particles (2.5 mass %) caused a decrease of this coefficient. It could be supposed that an increase of slurry viscosity affected the decrease of the volumetric mass transfer coefficient at higher solid concentration. An empirical correlation was proposed for volumetric mass transfer coefficient prediction. Its parameters were fitted using experimental data. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Reduced graphene oxide as a solid-state electron mediator in Z-scheme photocatalytic water splitting under visible light

The effectiveness of reduced graphene oxide as a solid electron mediator for water splitting in the Z-scheme photocatalysis system is demonstrated. We show that a tailor-made, photoreduced graphene oxide can shuttle photogenerated electrons from an O(2)-evolving photocatalyst (BiVO(4)) to a H(2)-evolving photocatalyst (Ru/SrTiO(3):Rh), tripling the consumption of electron-hole pairs in the water splitting reaction under visible-light irradiation.     

低对称性硫代烃基四氮杂卟啉的合成、表征及电化学性质研究

合成了硫代烃基四氮杂卟啉2,3,7,8,12,13-六(甲硫基)-17,18-一(二噻英)四氮杂卟啉[H₂Pz(dtn)(mt)₆]及其过渡金属配合物MPz(dtn)(mt)₆,由元素分析、质谱、¹HNMR、UV-Vis和IR光谱对其组成和结构进行了表征,通过循环伏安测试结果讨论了H₂Pz(dtn)(mt)₆的电化学性质,证明H₂Pz(dtn)(mt)₆的还原过程为单电子连续传输过程,属于CE机理.研究了H₂Pz(dtn)(mt)₆对正极材料MnO₂在锂离子电池中的修饰作用.结果表明,H₂Pz(dtn)(mt)₆对改善锂离子电池的初始充放电容量和循环次数都有明显的增加.     

加温加压条件下气液固三相鼓泡塔体积传质系数的测定

气液固三相鼓泡塔反应器被广泛地应用于化工、石油化工、煤化工、化工冶金、环境工程等领域,如石油馏分的加氢、煤的脱硫与脱氮、对二甲苯氧化、费托合成、甲醇合成、二甲醚合成以及含有机物废水的湿式氧化等工业过程[1.2].     

以Fe2O3为原料制备LiFePO4/C复合材料及其性能研究

以Fe2O3为铁源原料, 利用热还原法成功地制备了LiFePO4/C复合材料. 用XRD以及SEM对材料的晶体结构以及表面形貌进行了表征. 通过循环伏安和充放电测试研究了材料的电化学性能. 研究结果表明， 于700 ℃下制备的LiFePO4/C复合材料在0.1C的倍率下可以得到放电容量144.8 mA·h/g, 在循环160次后, 容量仍保持在141.4 mA·h/g. 这种以廉价的Fe2O3代替目前常用的二价铁盐原料方法, 具有减少LiFePO4合成成本的优点.     

Syntheses, characterization, and photo-hydrogen-evolving properties of tris(2,2'-bipyridine)ruthenium(II) derivatives tethered to a cis-Pt(II)Cl2 unit: insights into the structure-activity relationship

The photo-hydrogen-evolving activity (activity to enhance the photochemical EDTA-reduction of water into molecular hydrogen) was evaluated for three different Ru(II)Pt(II) dimers with a general formula of [(bpy)2Ru(micro-bridge)PtCl2]2+(bpy = 2,2'-bipyridine; bridge = 4,4'-bis(N-(3-aminopropyl)carbamoyl)-2,2'-bipyridine (L1), 2,3-bis(2-pyridyl)pyrazine (L2), and 4,4'-bis(N-(4-pyridyl)methylcarbamoyl)-2,2'-bipyridine (L3); EDTA = ethylenediaminetetraacetic acid disodium salt). A new Ru(II)Pt(II) complex, [(bpy)2Ru(micro-L3)PtCl2]2+, was synthesized and characterized. It was confirmed that all three compounds are ineffective towards photochemical H2 production. In each case, an acetate-buffer solution (pH = 5) containing the Ru(II)Pt(II) dimer and EDTA was photolysed using a 350-W Xe lamp under an Ar atmosphere, during which the amount of H2 evolved was analysed by gas chromatography. Additional photolysis experiments were carried out by adding [Ru(bpy)3]2+ and methylviologen (N,N'-dimethyl-4,4'-bipyridinium) to the photolysis solutions described above to test the H2-evolving activity of the Pt(II) unit involved in these Ru(II)Pt(II) dimers. As a result, the Pt(II) units involved in the L1 and L2 compounds were found to be active as an H2-evolving catalyst, while that of the L3 compound was found to show no activity at all. The extent of intramolecular electron-transfer quenching from the 3MLCT excited state of the [Ru(bpy)3]2+ derivative to the tethering Pt(II) catalyst centre was investigated by comparison of the luminescence spectra of these compounds, together with the related compounds. The results showed that the quenching of the 3MLCT luminescence is not at all enhanced in either the L1 or the L3 compounds. On the other hand, the L2 compound is strongly quenched as previously reported. In addition to the above studies, the H2-evolving activity of some Pt(II) monomers, cis-PtCl2(NH3)2, PtCl2(en)(en = ethylenediamine), cis-PtCl2(4-methylpyridine)2, PtCl2(2,2'-bipyrimidine), PtCl2(4,4'-dicarboxy-2,2'-bipyridine), and [PtCl(terpy)]+(terpy = 2,2':6',2'-terpyridine), were similarly investigated in the presence of EDTA, [Ru(bpy)3]2+ and methylviologen, since they were regarded as structural analogues of the Pt(II) units involved in the L1-L3 compounds. The compounds having a cis-Pt(II)Cl2 unit were generally found to show high H2-evolving activity. This was interpreted in terms of the ligation of negatively charged chloride anions leading to the destabilization of the Pt(II) dz2 orbital responsible for the hydrogenic activation. Importantly, cis-PtCl2(4-methylpyridine)2 exhibited relatively high activity as an H2-evolving catalyst, suggesting the importance of the flexible rotation of the pyridyl ligands for efficient hydrogenic activation at the axial site of the Pt(II) ion. The DFT calculations also showed the validity of the structure-activity relationship discussed above for the L3 compound.     

Study on the time-dependent simulation and input parameter sensitivity of spent nuclear fuel electrorefining

A computer program for the simulation of spent nuclear fuel electrorefining has been developed based on general Butler–Volmer kinetics and mass transport within a diffusion layer model. The effect of a solid electrode area change due to the dissolution and deposition, the solubility of the element in the liquid Cd, and a volume change due to the development of metallic compounds were considered in this program. The program has been verified through Tomczuk et al.’s experiment, and the results show a good agreement of within 4 and 2 % for U amount in the anode and cathode, respectively. The sensitivity of several input parameters such as the standard electrode potential, activity coefficient, diffusion coefficient, diffusion layer thickness, and transfer coefficient has been tested. It was found that the standard electrode potential is very sensitive, as a 3 % variation leads to a U amount change of more than 30 and 50 % in the anode and molten salt, respectively. The sensitivity of the other input parameters is much less than the standard electrode potential, but significant within the data difference with the other references, except for the transfer coefficient. This result is useful for understanding the effectiveness of each input parameters on the simulation results.     

Laser flash photolysis and magnetic field effect studies on the interaction of uracil and its derivatives with menadione and 9,10-anthraquinone

Laser flash photolysis and an external magnetic field have been used to study the interaction of two quinone molecules, namely, 9,10-anthraquinone (AQ) and 2-methyl-1,4-naphthoquinone, commonly known as menadione (MQ), with the RNA base uracil (U) and two of its derivatives, 1,3-dimethyluracil (dmU) and uridine (dU). We have conducted our studies in homogeneous organic and heterogeneous micellar media in order to investigate the effect of media on the molecules and any change in reactivity on account of substitution. In organic homogeneous medium, both the quinones have behaved similarly with the bases. Here U has undergone both electron transfer (ET) and hydrogen (H) transfer, while dU and dmU have failed to exhibit any ET. Failure to support ET has been attributed to keto-enol tautomerism, which has been found to have a significant role in determining the occurrence of ET from these pyrimidine bases. However, in SDS micelles some variations regarding the reactivity of these molecules have been discerned. The variations are 2-fold. Here ET from U has been found to get completely eclipsed by a dominant H abstraction with both the quinones, and AQ reveals a difference in the extent of H abstraction with the bases in SDS. With U and dU, the prevailing H abstraction with AQ has succeeded in formation of only AQH(*), while dmU has produced both AQH(*) and AQH(2), the latter being formed by two successive H abstraction. Explanations of this intriguing behavior with U and its derivatives with quinone molecules have been the main concern in this work.     

阳极支撑层憎水性对被动式直接甲醇燃料电池传质性能的影响

通过测定甲醇渗透率,详细研究了阳极支撑层的聚四氟乙烯（PTFE）含量对全被动式直接甲醇燃料电池（DMFC）甲醇传质和电池性能的影响。 膜电极集合体均使用相同的阳极催化层,膜和阴极。 实验结果表明,随着阳极支撑层PTFE含量的提高,甲醇渗透速率明显减小。 其含量较高时,甲醇传质阻力较大,会导致电池在很低的电流密度下就出现传质控制区。 采用PTFE质量分数为40%的支撑层时,DMFC以9 mol/L甲醇为燃料最大功率密度可达32×10-3 W/cm2,也进一步证明了适当提高阳极支撑层的憎水性,既有助于减少甲醇的渗透,又缓解了阴极的“水淹”问题。     

Liquid phase deposition of hemoglobin/SDS/TiO2 hybrid film preserving photoelectrochemical activity

This work demonstrates that liquid phase deposition (LPD) technique provides a novel approach to the immobilization of hemoglobin (Hb) in TiO(2) film for studying the direct electron transfer of Hb. Using the LPD process, a hybrid film composed of Hb, TiO(2) and sodium dodecylsulfonate (SDS) is successfully prepared on the electrode surface. The surface morphology of as-deposited Hb/SDS/TiO(2) film shows a flower-like structure. The cyclic voltammetric measurement indicates that the LPD hybrid film facilitates the electron transfer of Hb, which yields a pair of redox peaks prior to the characteristic voltammetric peaks of TiO(2). Due to the electrocatalytic activity of Hb towards H(2)O(2), the Hb/SDS/TiO(2) hybrid LPD film can be utilized as an H(2)O(2) sensor, showing a sensitive response linearly proportional to the concentration of H(2)O(2) in the range of 5.0×10(-7)-4.0×10(-5) mol/L. At the same time, the Hb/SDS/TiO(2) hybrid film preserves the photoelectrochemical activity of TiO(2). The photovoltaic effect on the electrochemical behavior of Hb/SDS/TiO(2) film is observed after long-time UV irradiation on the film, which could improve the calibration sensitivity for H(2)O(2).     

Membrane extraction for separation of copper cations from acid solution using polypropylene hollow fibre membrane

The membrane extraction of copper ions was carried out using hydrophobic poly(propylene) (PP) hollow fiber membrane modules and kerosene solutions containing organic extractant. The influences of different extractant on the extraction yield, mass transfer performance and mass transfer mechanism were studied. Compared with 2‐ethylhexyl phosphoric acid (2EHPA) and 2‐methyl‐5‐sulpho benzaldoxime (2M5SB), di‐(2‐ethylhexyl)phosphoric acid (D2EHPA) extractant system with high distribution coefficient exhibited higher extraction yield of 99.7%. The extraction equilibrium time, the final extraction yield and the total mass transfer coefficient were independent of the flow rates of two phases. The extraction equilibrium time and the final extraction yield at different flow rates of two phases were 80 min and near 99.5%, respectively. A mass transfer model of a complexation reaction describing the overall mass transfer resistance was controlled by interfacial reactions rather than the aqueous and organic boundary layer which could explain the effect of flow rate on the final extraction yield and the total mass transfer coefficient. This model showed that the mass transfer resistance and mass transfer coefficient were independent of Cu²⁺ when copper ion concentration was more than 0.06 g/L. However, when copper concentration was less than 0.06 g/l, the mass transfer resistance increased as Cu²⁺ concentration decreased, and the mass transfer coefficient decreased as Cu²⁺ concentration decreased. Extractant entrainment in the aqueous phase and membrane fouling were investigated primarily. It was found that the solvent entrainment could reduce to 10 ppm much lower than 200 ppm of the classic liquid–liquid extraction, and that the cleaning of contaminated membranes was not complete. However, it can be still concluded from this research that the membrane extraction in PP hollow fibre with D2EHPA extractant would be an effective and promising processing means for Cu²⁺ separation from aqueous solution. Copyright © 2005 John Wiley & Sons, Ltd.     

Micelle-induced versatile performance of amphiphilic intramolecular charge-transfer fluorescent molecular sensors

A series of amphiphilic intramolecular charge-transfer fluorescent molecular sensors AS1-3, equipped with a rod-shaped hydrophobic 2-phenylbenzoxazole fluorophore and a hydrophilic tetraamide Hg(2+)-ion receptor, have been prepared. These sensor molecules could be incorporated into the hydrophobic sodium dodecyl sulfate (SDS) micelle, which is confirmed by the clear spectral blue shift and emission enhancement observed at the critical micelle concentration of SDS. Systematic examination of the sensor-Hg(2+) complexation, by using both UV/visible and fluorescence spectroscopy, indicates that SDS significantly modulates both the binding event and signal transformation of these sensor molecules. The potential advantages are fourfold: 1) SDS substantially increases the Hg(2+)-ion association constant and results in an amplified sensitivity. 2) SDS initiates spectral features which facilitate Hg(2+)-ion analysis, for example, in addition to the strengthened fluorescence of the free sensors AS1-3, the original "on-off" response of AS2 toward the Hg(2+) ion is transformed into a self-calibrated two-wavelength ratiometric signal, while for AS3, Hg(2+)-ion complexation in the presence of SDS results in a 180 nm blue shift, which is preferred to the 51 nm spectral shift obtained without SDS. 3) Thermoreversible tuning of the dynamic detection range is realized. 4) Highly specific Hg(2+)-ion identification could be achieved by using the SDS-induced fingerprint emission (358 nm) of the AS2-Hg(2+) complex. Altogether, this work demonstrates a convenient and powerful strategy that remarkably elevates the performance of a given fluorescent molecular sensor. It also implies that for a specific utilization, much attention should be paid to the microenvironment in which the sensor resides, as the behavior of the sensor might be different from that in the bulk solution.     

光敏络合催化光解水析氢的电化学模拟

Durham等^[1]曾利用Pt(黑)|lN HCl‖Ru(bipy)₃²⁺、MV²⁺、EDTA(pH=9)|Pt(网)电池模拟光解水析氢反应。但该装置的左、右二半电池中溶液的pH值相差9以上,相当于外加0.5V以上的偏压,因此,不能真实地模拟自发的光解水析氢过程。     

阴离子表面活性剂存在下光系统II中酪氨酸残基的性能研究

通过荧光光谱和富立叶变换红外(FT-IR)光谱研究了阴离子型表面活性剂－十 二烷基硫酸钠（SDS）与光系统II（PSII）的相互作用。结果表明,PSII表现出酪 氨酸荧光的特性。在PSII蛋白质内部,存在着232 nm处的组分与酪氨酸之间以及这 两种氨基酸列基与叶绿素a之间的能量传递。SDS的存在会使这些能量传递以及 PSII中蛋白的骨架结构和酪氨酸残基的结构发生改变,而变化方式又明显受SDS在 溶液中聚集状态的影响。低于其临界胶束浓度(cmc)时,SDS会促进蛋白质中232 nm外的组分与酪氨酸之间的能量传递,并且使酪氨酸残基外于极性更小的环境; 而大于cmc时,SDS却产生相反的效应。但不同浓度的SDS均会抑制酪氨酸残基至叶 绿素a的能量传递。     

Characteristics of an integrated cathode assembly for the electrolytic reduction of uranium oxide in a LiCl-Li2O molten salt

Summary Electrochemical behavior of the reduction of uranium oxide was studied in a LiCl-Li₂O molten salt system with an integrated cathode assembly. The mechanism for the electrolytic reduction of uranium oxide was studied through cyclic voltammetry. By means of a chronopotentiometry, the effects of the thickness of the uranium oxide, the thickness of the MgO membrane and the material of the conductor of an integrated cathode assembly on the overpotential of the cathode were investigated. From the voltamograms, the reduction potential of the uranium oxide and Li₂O was obtained and the two mechanisms of the electrolytic reduction were considered with regard to the applied cathode potential. From the chronopotentiograms, the exchange current, the transfer coefficient and the maximum allowable current based on the Tafel behavior were obtained with regard to the thickness of the uranium oxide, and of the MgO membrane and the material of the conductor of an integrated cathode assembly.